Branched succinimide dispersant compounds and methods of making the compounds

ABSTRACT

In accordance with the disclosure, one aspect of the present application is directed to a dispersant compound comprising the reaction product of (i) a hydrocarbyl carbonyl compound, (ii) a polycarbonyl compound having at least three carbonyl acylating functions, and (iii) a primary amine moiety of a polyamine. Methods of making and methods of using the dispersant compound are also disclosed.

RELATED APPLICATIONS

The present application claims the benefit of priority to U.S.NonProvisional patent application Ser. No. 11/548,151 filed on Oct. 10,2006, the specification and claims of which are herein incorporated byreference.

DESCRIPTION OF THE DISCLOSURE

1. Field of the Disclosure

The present application is directed to dispersant compounds and methodsfor making the dispersant compounds, and more specifically, todispersant compounds that can be employed in fuel and lubricantcompositions.

2. Background of the Disclosure

Considerable effort has been expended to develop chemical products asdispersant additives for internal combustion engines. Oil-solubledispersants for lubricating oil have been developed to control depositand varnish formation, and to keep sludge and other solid matter, suchas oxidized base oil, in suspension in the lubricating oil. Dispersants,when added to hydrocarbon fuels employed in the engines, effectivelyreduce deposit formation that ordinarily occurs in carburetor ports,throttle bodies, venturies, intake ports and intake valves. Thereduction of these deposit levels has resulted in increased engineefficiency and a reduction in the level of hydrocarbon and carbonmonoxide emissions.

Despite the advances in the use of dispersants as oil and fueladditives, there remains a need for continued improvements in theability of dispersants to suspend sludge and/or disperse particulates.Thus, novel compounds exhibiting improved dispersant characteristics aredesired.

SUMMARY OF THE DISCLOSURE

In accordance with the disclosure, one aspect of the present applicationis directed to a dispersant compound comprising the reaction product of(i) a hydrocarbyl carbonyl compound, (ii) a polycarbonyl compound havingat least three carbonyl acylating functions, and (iii) a primary aminemoiety of a polyamine.

Another aspect of the present application is directed to a process forforming a dispersant compound. The process comprises reacting apolycarbonyl compound having at least three carbonyl functions with aprimary amine moiety of a polyamine to form a polyamine polyamideintermediate. The intermediate is reacted with a hydrocarbyl carbonylcompound.

Another aspect of the present application is directed to a polyaminepolyamide intermediate compound formed by reacting a polycarbonylcompound having at least three carbonyl functions with a primary aminemoiety of a polyamine.

Another aspect of the present application is directed to a polyaminepolyamide compound of formula III,

where n ranges from 0 to 10, and R⁹, R¹⁰, R¹¹, R¹² and R¹³ areindependently chosen from OH, a polyamine group, or a salt of thepolyamine group, with the proviso that at least one of R⁹, R¹⁰, R¹¹, R¹²and R¹³ is a polyamine group.

Another aspect of the present application is directed to a method offorming a polyamine polyamide intermediate compound. The methodcomprises reacting a polycarbonyl compound having at least threecarbonyl acylating functions with a primary amine moiety of a polyamine.

Another aspect of the present application is directed to a process forforming a dispersant compound. The process comprises reacting ahydrocarbyl carbonyl compound with a primary amine moiety of a polyamineto form a mono-succinimide amine intermediate. The mono-succinimideamine intermediate is reacted with a a polycarbonyl compound having atleast three carbonyl functions.

Another aspect of the present application is directed to a polyaminepolyamide succinimide of formula VI:

wherein n ranges from 0 to 10, and R²⁵, R²⁶, R²⁷, R²⁸ and R²⁹ areindependently chosen from a polyamine succinimide group or a polyaminesuccinimide group salt, with the proviso that at least R²⁵, R²⁶, R²⁷,R²⁸ and R²⁹ is a polyamine succinimide group.

Another aspect of the present application is directed to a lubricatingcomposition comprising a base oil; and a dispersant compound of thepresent application.

Another aspect of the present application is directed to a method ofreducing deposits on a lubricated surface, the method comprisinglubricating the surface with a lubricating composition of the presentapplication, wherein a dispersant compound of the present application ispresent in the lubricating composition in an amount sufficient to reducethe amount of deposits on the lubricated surface, as compared to theamount of deposits on the surface subjected to the same operatingconditions and lubricated with the same lubricant composition exceptthat the composition is devoid of the dispersant compound.

Another aspect of the present application is directed to a method forimproving the suspension of sludge comprising providing to a combustionsystem a lubricating composition of the present application, wherein thedispersant compounds are present in an amount sufficient to maintain atleast some sludge in suspension in the base oil for a period of timelonger than if the base oil did not contain the dispersant compounds.

Another aspect of the present application is directed to a lubricantadditive package composition comprising a diluent; and a dispersantcompound of the present application.

Another aspect of the present application is directed to fuelcomposition comprising a base fuel; and a dispersant compound of thepresent application.

Another aspect of the present application is directed to a method ofreducing deposits in the fuel system of an internal combustion engine,the method comprising using as the fuel for the internal combustionengine a fuel composition of the present application, wherein adispersant compound of the present application is present in the fuel inan amount sufficient to reduce the deposits in the fuel system, ascompared to the amount of deposits in the fuel system operated in thesame manner and using the same fuel composition except that the fuelcomposition is devoid of the dispersant compound.

Another aspect of the present application is directed to a method ofdispersing soot, comprising providing to a combustion system a fuelcomposition of the present application. A dispersant compound of thepresent application is present in the fuel composition in an amountsufficient to maintain at least some soot in suspension in the base fuelfor a period of time longer than if the base fuel did not contain thedispersant compound.

A fuel additive package composition comprising a diluent; and adispersant compound of the present application.

Additional aspects and advantages of the disclosure will be set forth inpart in the description which follows, and can be learned by practice ofthe disclosure. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the disclosure, as claimed.

DESCRIPTION OF THE EMBODIMENTS

The present application is directed to the preparation of noveldispersant compounds and their uses. In one aspect of the presentapplication, the dispersant compounds comprise the reaction product of(i) a hydrocarbyl carbonyl compound, (ii) a polycarbonyl compound havingat least three carbonyl acylating functions, and (iii) a primary aminemoiety of a polyamine. The dispersant compounds of the presentapplication have extended polar regions, which can result in one or moreadvantages, such as, for example, improved dispersant function in fueland/or lubricating compositions.

In some aspects, the dispersant compounds of the present application aremade by preparing a polyamine polyamide intermediate, which is reactedwith a hydrocarbyl carbonyl compound. The intermediate can be preparedby reacting a polycarbonyl compound having at least three carbonylacylating moieties with a primary amine moiety of a polyamine. Othersuitable methods for forming the dispersant compounds of the presentapplication may be employed, as will be discussed in greater detailbelow.

Polycarbonyl Compounds

The polycarbonyl reactant compounds used to form the polyamine polyamideintermediates of the present application can include any suitableorganic compound that has at least three carbonyl acylating groups, andthat is capable of reaction to form amides. In some embodiments, thepolycarbonyl compound can include one or more tertiary nitrogen atoms.Examples of such polycarbonyl compounds include, but are not limited to,amine polycarboxylic acids or esters, of the following formula I:

wherein n can range from 0 to about 10, and R¹, R², R³, R⁴ and R⁵ areindependently chosen from a hydrogen atom and C₁ to C₁₀ linear orbranched alkyl groups, such as methyl, ethyl and butyl. Non-limitingexamples of the carbonyl compounds of Formula I include ethylene diaminetetra acetic acid (EDTA), diethylene triamine pentaacetic acid, as wellas methyl, ethyl, propyl and butyl esters of these acids.

In one embodiment of the compound of formula I, at least one or more ofR¹, R², R³, R⁴ and R⁵ are chosen to be C₁ to C₁₀ linear or branchedalkyl groups. For example, the compound of formula I can be a mono, di,tri, or tetra ester of ethylene diamine tetra acetic acid. The ester canbe formed by any suitable method. For example, an acid or salt offormula I, such as EDTA or a sodium salt of EDTA, can be reacted with analcohol in the presence of an acid which can act as an esterificationcatalyst. Examples of suitable alcohols include methanol, ethanol,propanol and butanol. Examples of suitable esterification catalyst acidsinclude sulfuric acid, methanesulfonic acid, toluenesulfonic acid,hydrogen chloride.

In other embodiments, the polycarbonyl compound can be a compound otherthan the compounds of formula I. For example, in one aspect, thepolycarbonyl compound can be a carboxylic acid having at least threecarbonyl acylating functions, or esters thereof, which does not containa tertiary nitrogen, such as, citric acid or esters of citric acid.

Polyamine Compounds

In some aspects, the polyamine reactant used to form the polyaminepolyamide intermediate of the present application can be a linear,branched or cyclic polyalkyleneamine having at least one primary aminemoiety. For example, the polyamine can be a polyalkyleneamine of thefollowing Formula II:

wherein R⁶ can be a hydrogen atom or a low molecular weight alkyl grouphaving from about 1 to about 6 carbon atoms, m can be an integer rangingfrom about 1 to about 3 and n can be an integer ranging from about 2 toabout 10. Non-limiting examples of R⁶ alkyl groups include methyl,ethyl, propyl or butyl.

Non-limiting examples of suitable polyamines include propylene diamine,butylene diamine, diethylene triamine (DETA), triethylene tetramine(TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA),hexaethyleneheptamine (HEHA), dipropylene triamine and tripropylenetetramine. The polyamines can include linear, branched or cycliccompounds, or mixtures thereof. In one aspect, the polyamine is apolyethyleneamine, such as DETA, TETA, TEPA, PEHA, and HEHA. In oneaspect, the polyamine can be a copolymer of any one of the foregoingpolyethyleneamines ranging in molecular weight from about 100 to about600.

In some aspects, the polyamines can include mixtures of two or morepolyamine compounds, such as mixtures of two or more compounds chosenfrom TEPA, PEHA, HEHA, and higher molecular weight polyethyleneamineproducts. In some aspect, the mixture can comprise heavy polyamines. Aheavy polyamine is a mixture of polyalkyleneamines comprising smallamounts of lower amine oligomers such as TEPA and PEHA but primarilyoligomers with 7 or more nitrogen atoms, 2 or more primary amines permolecule, and more extensive branching than conventional amine mixtures.

Any suitable reaction conditions can be employed which result in thedesired intermediate compound. In one aspect, the polycarbonyl compoundcan be heated to a temperature ranging from about 100° C. to about 125°C. in a relatively inert atmosphere, such as under vacuum or in nitrogengas. The polyamine can then be mixed with the heated polycarbonyl. Inthis aspect, reaction times can range from about 1 hour to about 5hours. The reaction can be run neat or with solvents. Any water orsolvent can be removed to provide the desired polyamine polyamideintermediate.

The ratio of polycarbonyl reactant to polyamine reactant can be basedupon the ratio of the carbonyl moieties to primary amine moieties in thereactants. This carbonyl to primary amine ratio can be any suitableratio, such that there remains at least one unreacted primary aminemoiety in the intermediate. In one embodiment, the ratio of polycarbonylcompounds to primary amine compounds can range from about 1:1 to about1:5.

The resulting intermediate compound comprises an alkyl or alkylaminebackbone having one or more polyamine polyamide groups, and optionallyone or more carboxyl functional groups and/or carboxylate moieties. Forexample, the intermediate compound can be a compound of formula III,

where n ranges from 0 to 10, and R⁹, R¹⁰, R¹¹, R¹² and R¹³ areindependently chosen from a hydroxyl group, a polyamine group, or apolyamine salt group (e.g., —O⁻⁺H-TEPA), with the proviso that at leastone of R⁹, R¹⁰, R¹¹, R¹² and R¹³ is a polyamine group. The polyaminegroups and polyamine salt groups can be derived from any of thepolyamine compounds described above. Examples of such groups includepropylene diamine groups, butylene diamine groups, diethylene triamine(DETA) groups, triethylene tetramine (TETA) groups, tetraethylenepentamine (TEPA) groups, pentaethylene hexamine (PEHA) groups,hexaethyleneheptamine (HEHA) groups, dipropylene triamine groups andtripropylene tetramine groups, and salts of these groups. Where R⁹, R¹⁰,R¹¹, R¹² or R¹³ is a polyamine group, a primary amine nitrogen atom ofthe polyamine links with the corresponding carbonyl acylating group offormula III to form an amide.Hydrocarbyl Carbonyl Compound

The hydrocarbyl carbonyl reactant compound of the present applicationcan be any suitable compound having a hydrocarbyl moiety and a carbonylmoiety, and that is capable of bonding with the polyamine polyamideintermediate compound to form the dispersant compounds of the presentapplication. Non-limiting examples of suitable hydrocarbyl carbonylcompounds include, but are not limited to, hydrocarbyl substitutedsuccinic anhydrides, hydrocarbyl substituted succinic acids, and estersof hydrocarbyl substituted succinic acids. Specific examples includesuch compounds as dodecenylsuccinic anhydrides, C₁₆₋₁₈ alkenyl succinicanhydride, and polyisobutenyl succinic anhydride (PIBSA). In someembodiments, the PIBSA may have a polyisobutylene portion with amolecular weight ranging from about 200 to about 6000 daltons and avinylidene content ranging from about 4% to greater than about 90%. Insome embodiments, the ratio of the number of carbonyl groups to thenumber of hydrocarbyl moieties in the hydrocarbyl carbonyl compound canrange from about 1:1 to about 6:1.

As used herein, the term “hydrocarbyl group” or “hydrocarbyl” is used inits ordinary sense, which is well-known to those skilled in the art.Specifically, it refers to a group having a carbon atom directlyattached to the remainder of a molecule and having a predominantlyhydrocarbon character. Examples of hydrocarbyl groups include:

(1) hydrocarbon substituents, that is, aliphatic (e.g., alkyl oralkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, andaromatic-, aliphatic-, and alicyclic-substituted aromatic substituents,as well as cyclic substituents wherein the ring is completed throughanother portion of the molecule (e.g., two substituents together form analicyclic radical);

(2) substituted hydrocarbon substituents, that is, substituentscontaining non-hydrocarbon groups which, in the context of thedescription herein, do not alter the predominantly hydrocarbonsubstituent (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy,mercapto, alkylmercapto, nitro, nitroso, and sulfoxy);

(3) hetero-substituents, that is, substituents which, while having apredominantly hydrocarbon character, in the context of this description,contain other than carbon in a ring or chain otherwise composed ofcarbon atoms. Hetero-atoms include sulfur, oxygen, nitrogen, andencompass substituents such as pyridyl, furyl, thienyl, and imidazolyl.In general, no more than two, or as a further example, no more than one,non-hydrocarbon substituent will be present for every ten carbon atomsin the hydrocarbyl group; in some embodiments, there will be nonon-hydrocarbon substituent in the hydrocarbyl group.

In some aspects, the hydrocarbyl carbonyl compound can be a polyalkylenesuccinic anhydride reactant having the following Formula IV:

wherein R¹⁴ is a hydrocarbyl moiety, such as for example, a polyolefinradical having a number average molecular weight of from about 350 toabout 10,000 daltons. For example, the number average molecular weightof R¹⁴ can range from about 1000 to about 5000 daltons as measured byGPC. Unless indicated otherwise, molecular weights in the presentspecification are number average molecular weights.

In some aspects, R¹⁴ can be a polyolefin radical comprising one or morepolymer units chosen from linear or branched alkenyl units. In someaspects, the alkenyl units can have from about 2 to about 10 carbonatoms. For example, the polyolefin radical can comprise one or morelinear or branched polymer units chosen from ethylene radicals,propylene radicals, butylene radicals, pentene radicals, hexeneradicals, octene radicals and decene radicals. In some aspects, R¹⁴ canbe a polyolefin radical in the form of, for example, a homopolymer,copolymer or terpolymer. For example, the polyolefin radical can be acopolymer of ethylene and propylene. In another example, the polyolefinradical is a homopolymer of polyisobutylene. The polyolefin compoundsused to form the R¹⁴ polyolefin radicals can be formed by any suitablemethods, such as by conventional catalytic oligomerization of alkenes.

In some aspects, high reactivity polyisobutenes having relatively highproportions of polymer molecules with a terminal vinylidene group can beused to form the hydrocarbyl substituent. In one example, at least 4% ofthe total terminal olefinic double bonds in such high reactivitypolyisobutenes can be a methylvinylidene isomer. In other examples, 50%or more of the total terminal olefinic double bonds can bemethylvinylidene isomers, such as at least 70%. Well known highreactivity polyisobutenes are disclosed, for example, in U.S. Pat. No.4,152,499, the disclosure of which is herein incorporated by referencein its entirety.

The hydrocarbyl carbonyl compounds can be made using any suitablemethod. Methods for forming hydrocarbyl carbonyl compounds are wellknown in the art. One example of a known method for forming ahydrocarbyl carbonyl compound comprises blending a polyolefin and maleicanhydride. The polyolefin and maleic anhydride reactants are heated totemperatures of, for example, about 150° C. to about 250° C.,optionally, with the use of a catalyst, such as chlorine or peroxide.

The hydrocarbyl carbonyl compound can be combined with the polyaminepolyamide intermediate under any suitable reaction conditions that willresult in the desired dispersant compound of the present application.For example, the hydrocarbyl carbonyl can be heated to a temperatureranging from about 100° C. to about 160° C. under nitrogen. Thepolyamine polyamide intermediate can then be added. The reactant mixturecan be stirred and heated at temperatures ranging from about 140° C. toabout 200° C. under reduced pressure for about 2 hours to about 6 hours.The reaction can be run neat or with solvents and/or diluents, such asprocess oil. After the reaction is completed the mixture can be dilutedwith process oil and filtered to afford the desired dispersant.

In an alternative embodiment, the reaction of the polycarbonyl,polyamine, and hydrocarbyl carbonyl compounds may be carried out in adifferent order than is described above. For example, instead ofreacting a polycarbonyl compound and a polyamine compound to form theabove described polyamine polyamide intermediate, the hydrocarbylcarbonyl compounds described above can be reacted with the polyaminecompounds described above to form a mono-succinimide amine intermediate.Examples of such mono-succinimide amine intermediates can be of thefollowing formula V.

where R⁶, R¹⁴, m and n are as defined above.

The reaction of the hydrocarbyl carbonyl and polyamine compounds can becarried out under any conditions that will result in the desiredmono-succinimide compounds. For example a 1:1 molar equivalent of ahydrocarbyl carbonyl compound and polyamine can be blended and heated totemperatures ranging from, for example, about 120° C. to about 250° C.

The mono-succinimide amine intermediate can then be reacted with thepolycarbonyl ester compounds described above, such as the esters offormula I or esters of carboxylic acids, to form the desired dispersantcompounds of the present application. The reaction can be carried out byblending any suitable amounts of the mono-succinimide amine intermediateand polycarbonyl ester compounds under suitable process conditions. Forexample, the ratio of mono-succinimide amine intermediate topolycarbonyl ester compound can range from about 2.7:1 to about 4:1. Thereaction can be performed under conditions necessary to react an aminewith an ester to form an amide bond. For example, the reaction can beperformed neat or in a process oil at a temperature ranging from about100° C. to about 180° C.

Polyamine Polyamide Succinimide Compounds

In some aspects, the dispersant compounds of the present application cancomprise polyamine polyamide succinimide compounds. The polyaminepolyamide succinimide dispersant compounds of the present applicationcomprise an alkyl or alkylamine backbone having one or more polyaminepolyamide succinimide groups, and optionally one or more carboxylatefunctional groups and/or polyamine polyamide succinimide salts.Non-limiting examples of the polyamine polyamide succinimide compoundsinclude compounds of formula VI:

wherein n ranges from 0 to 10, and R²⁵, R²⁶, R²⁷, R²⁸ and R²⁹ areindependently chosen from a polyamine succinimide group or a polyaminesuccinimide group salt (e.g., —O⁻⁺H-TEPA succinimide group), with theproviso that at least one of R²⁵, R²⁶, R²⁷, R²⁸ and R²⁹ is a polyaminesuccinimide group.

In one aspect of the application, R²⁵, R²⁶, R²⁷, R²⁸ and R²⁹ areindependently chosen from polyamine succinimide groups of the formulaVII, and salts thereof:

wherein R⁶, R¹⁴, m and n are defined as above. Non-limiting examples ofsuch polyamine succinimide groups include propylene diamine succinimidegroups, butylene diamine succinimide groups, diethylene triamine (DETA)succinimide groups, triethylene tetramine (TETA) succinimide groups,tetraethylene pentamine (TEPA) succinimide groups, pentaethylenehexamine (PEHA) succinimide groups, hexaethyleneheptamine (HEHA)succinimide groups, dipropylene triamine succinimide groups andtripropylene tetramine succinimide groups, and salts of these groups.

The dispersant compounds of the present application are useful asdispersants in lubricant compositions. Accordingly, one aspect of thepresent application relates to a lubricating oil composition comprisinga major amount of an oil of lubricating viscosity and an amount of adispersant compound of the present application sufficient to providedispersancy. The term “major amount” as used herein means an amountgreater than or equal to 50% by weight relative to the total weight ofthe composition.

When the dispersant compounds of this application are used in lubricantcompositions, they can be present in any suitable amount. In oneexample, the dispersant compounds can be present in an amount of fromabout 0.1 to about 20% by weight of the total composition, such as fromabout 0.5 to about 15% by weight, and in another example, from about 1to about 7% by weight.

The lubricating compositions disclosed herein can comprise a base oil.Base oils suitable for use in formulating the disclosed compositions canbe selected from, for example, synthetic or mineral oils, or mixturesthereof.

The base oil can be present in a major amount, wherein “major amount” isunderstood to mean greater than or equal to 50% by weight of thelubricant composition, such as from about 80% to about 98% by weight ofthe lubricant composition. The base oil typically has a viscosity of,for example, from about 2 to about 15 cSt and, as a further example,from about 2 to about 10 cSt at 100° C.

Non-limiting examples of mineral oils suitable as base oils includeanimal oils and vegetable oils (e.g., castor oil, lard oil) as well asother mineral lubricating oils such as liquid petroleum oils and solventtreated or acid-treated mineral lubricating oils of the paraffinic,naphthenic or mixed paraffinic-naphthenic types. Oils derived from coalor shale are also suitable. Further, oils derived from a gas-to-liquidprocess are also suitable.

Non-limiting examples of synthetic oils include hydrocarbon oils such aspolymerized and interpolymerized olefins (e.g., polybutylenes,polypropylenes, propylene isobutylene copolymers, etc.);polyalphaolefins such as poly(1-hexenes), poly-(1-octenes),poly(1-decenes), etc. and mixtures thereof; alkylbenzenes (e.g.,dodecylbenzenes, tetradecylbenzenes, di-nonylbenzenes,di-(2-ethylhexyl)benzenes, etc.); polyphenyls (e.g., biphenyls,terphenyl, alkylated polyphenyls, etc.); alkylated diphenyl ethers andalkylated diphenyl sulfides and the derivatives, analogs and homologsthereof and the like.

Alkylene oxide polymers and interpolymers and derivatives thereof wherethe terminal hydroxyl groups have been modified by esterification,etherification, etc., constitute another class of known synthetic oilsthat can be used. Such oils are exemplified by the oils prepared throughpolymerization of ethylene oxide or propylene oxide, the alkyl and arylethers of these polyoxyalkylene polymers (e.g., methyl-polyisopropyleneglycol ether having an average molecular weight of about 1000, diphenylether of polyethylene glycol having a molecular weight of about500-1000, diethyl ether of polypropylene glycol having a molecularweight of about 1000-1500, etc.) or mono- and polycarboxylic estersthereof, for example, the acetic acid esters, mixed C₃₋₈ fatty acidesters, or the C₁₃ Oxo acid diester of tetraethylene glycol.

Another class of synthetic oils that can be used includes the esters ofdicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinicacids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid,sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonicacid, alkyl malonic acids, alkenyl malonic acids, etc.) with a varietyof alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol,2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether,propylene glycol, etc.) Specific examples of these esters includedibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctylsebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate,didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester oflinoleic acid dimer, the complex ester formed by reacting one mole ofsebacic acid with two moles of tetraethylene glycol and two moles of2-ethylhexanoic acid and the like.

Esters useful as synthetic oils also include those made from C₅₋₁₂monocarboxylic acids and polyols and polyol ethers such as neopentylglycol, trimethylol propane, pentaerythritol, dipentaerythritol,tripentaerythritol, etc.

Hence, the base oil used to make the compositions as described hereincan be selected from any of the base oils in Groups I-V as specified inthe American Petroleum Institute (API) Base Oil InterchangeabilityGuidelines. Such base oil groups are as follows:

Group I contain less than 90% saturates and/or greater than 0.03% sulfurand have a viscosity index greater than or equal to 80 and less than120; Group II contain greater than or equal to 90% saturates and lessthan or equal to 0.03% sulfur and have a viscosity index greater than orequal to 80 and less than 120; Group III contain greater than or equalto 90% saturates and less than or equal to 0.03% sulfur and have aviscosity index greater than or equal to 120; Group IV arepolyalphaolefins (PAO); and Group V include all other basestocks notincluded in Group I, II, III or IV.

The test methods used in defining the above groups are ASTM D2007 forsaturates; ASTM D2270 for viscosity index; and one of ASTM D2622, 4294,4927 and 3120 for sulfur.

Group IV basestocks, i.e. polyalphaolefins (PAO) include hydrogenatedoligomers of an alpha-olefin, the most important methods ofoligomerisation being free radical processes, Ziegler catalysis, andcationic, Friedel-Crafts catalysis.

The polyalphaolefins typically have viscosities in the range of 2 to 100cSt at 100° C., for example 4 to 8 cSt at 100° C. They can, for example,be oligomers of branched or straight chain alpha-olefins having fromabout 2 to about 30 carbon atoms; non-limiting examples includepolypropenes, polyisobutenes, poly-1-butenes, poly-1-hexenes,poly-1-octenes and poly-1-decene. Included are homopolymers,interpolymers and mixtures.

Regarding the balance of the basestock referred to above, a “Group Ibasestock” also includes a Group I basestock with which basestock(s)from one or more other groups can be admixed, provided that theresulting admixture has characteristics falling within those specifiedabove for Group I basestocks.

Exemplary basestocks include Group I basestocks and mixtures of Group IIbasestocks with Group I basestock.

Basestocks suitable for use herein can be made using a variety ofdifferent processes including but not limited to distillation, solventrefining, hydrogen processing, oligomerisation, esterification, andre-refining.

The base oil can be an oil derived from Fischer-Tropsch synthesizedhydrocarbons. Fischer-Tropsch synthesized hydrocarbons can be made fromsynthesis gas containing H₂ and CO using a Fischer-Tropsch catalyst.Such hydrocarbons typically require further processing in order to beuseful as the base oil. For example, the hydrocarbons can behydroisomerized using processes disclosed in U.S. Pat. No. 6,103,099 or6,180,575; hydrocracked and hydroisomerized using processes disclosed inU.S. Pat. No. 4,943,672 or 6,096,940; dewaxed using processes disclosedin U.S. Pat. No. 5,882,505; or hydroisomerized and dewaxed usingprocesses disclosed in U.S. Pat. No. 6,013,171; 6,080,301; or 6,165,949.

Unrefined, refined and rerefined oils, either mineral or synthetic (aswell as mixtures of two or more of any of these) of the type disclosedhereinabove can be used in the base oils. Unrefined oils are thoseobtained directly from a mineral or synthetic source without furtherpurification treatment. For example, a shale oil obtained directly fromretorting operations, a petroleum oil obtained directly from primarydistillation or ester oil obtained directly from an esterificationprocess and used without further treatment would be an unrefined oil.Refined oils are similar to the unrefined oils except they have beenfurther treated in one or more purification steps to improve one or moreproperties. Many such purification techniques are known to those skilledin the art such as solvent extraction, secondary distillation, acid orbase extraction, filtration, percolation, etc. Rerefined oils areobtained by processes similar to those used to obtain refined oils,where the processes are applied to refined oils which have been alreadyused in service. Such rerefined oils are also known as reclaimed orreprocessed oils and often are additionally processed by techniquesdirected to removal of spent additives, contaminants, and oil breakdownproducts.

The lubricant compositions of the present application can be used in anyengine or other combustion systems or mechanical devices that maybenefit therefrom. For example, the lubricant compositions can besuitable for use in the crank case of an internal combustion engine.

In some embodiments, the dispersant compounds of the present applicationcan be added to the lubricant composition in the form of a lubricantadditive package. Lubricant additive packages include concentratesdissolved in a diluent, such as mineral oil, synthetic hydrocarbon oils,and mixtures thereof. When blended with the base oil, these concentrateadditive compositions can provide an effective concentration of theadditives in the base oil. The amount of the dispersant compounds of thepresent application in the lubricant additive packages may vary fromabout 5 wt % to about 75 wt % of the concentrate additive composition,such as from about 5 wt % to about 50 wt %.

The lubricant additive package compositions and finished lubricants ofthe present application may contain other additional additives. Examplesof such additional additives include dispersants other than thedispersants of the present application, detergents, anti-wear agents,supplemental antioxidants, viscosity index improvers, pour pointdepressants, corrosion inhibitors, rust inhibitors, foam inhibitors, andfriction modifiers. Such additives are well known in the art, andchoosing effective amounts of additional additives in lubricantcompositions would be within the ordinary skill of the art.

In one aspect, the present application is directed to a method ofreducing deposits on a lubricated surface, wherein said method comprisesusing as the lubricating oil for said surface a lubricating oilcontaining the dispersant compound of the present invention. Thedispersant compound can be present in an amount sufficient to reduce theamount of deposits on the surface, as compared to the amount of depositsthat would be formed on the surface if it were subjected to the sameoperating conditions and using the same lubricating oil, except that theoil was devoid of the dispersant compound. Representative examples ofthe deposits that may be reduced using the compositions of the presentinvention include piston deposits, ring land deposits, crown landdeposits and top land deposits.

In another aspect, the present application is directed to a method forimproving the suspension of sludge in a lubricating oil. The methodcomprises providing to a combustion system the lubricating oils of thepresent application, wherein the dispersant compound is present in anamount sufficient to maintain at least some sludge in suspension in theoil for a period of time longer than if the oil did not contain thedispersant compound.

The dispersant compounds of the present application are also useful asdispersants in fuels. Thus, another aspect of the present application isa fuel composition comprising a major amount of a fuel and a minoramount of dispersant compounds of the present application sufficient toprovide a desired dispersancy. The concentration of the additive in afuel is dependent upon a variety of factors, including the type of fuelused, the presence of other dispersants or other additives, and thelike. Non-limiting example concentrations can range from about 10 toabout 10,000 weight parts per million, or from about 30 to about 5,000weight parts per million.

The base fuels used in formulating the fuel compositions of the presentinvention include any base fuels suitable for use in the operation ofspark-ignition or compression-ignition internal combustion engines suchas diesel fuel, jet fuel, kerosene, leaded or unleaded motor andaviation gasolines, and so-called reformulated gasolines which cancontain both hydrocarbons of the gasoline boiling range and fuel-solubleoxygenates, such as alcohols, ethers and other suitableoxygen-containing organic compounds. Examples of oxygenates suitable foruse in the present application include methanol, ethanol, isopropanol,t-butanol, mixed C₁ to C₅ alcohols, methyl tertiary butyl ether,tertiary amyl methyl ether, ethyl tertiary butyl ether and mixed ethers.Oxygenates, when used, can be present in the base fuel in an amountbelow, for example, about 25% by volume. In some embodiments, theoxygenates can be present in an amount that provides an oxygen contentin the overall fuel in the range of about 0.5 to about 5 percent byvolume.

The base fuels used in formulating the fuel compositions of the presentinvention can include, for example, compression ignition fuels having asulfur content of up to about 0.2% by weight, such as up to about 0.05%by weight, as determined by the test method specified in ASTM D 2622-98.In some embodiments, suitable compression-ignition fuels for use in thepresent invention are low sulfur content diesel fuels.

In yet another aspect of the present application, the dispersantcompounds are useful as fuel additive concentrates. The fuelconcentrates can comprise an inert stable organic solvent for a diluentand from about 5 to 50 weight percent of a dispersant compound of thepresent application. Non-limiting examples of suitable diluents includebenzene, toluene, xylene or higher boiling aromatics.

In one aspect, the present application is directed to a method ofreducing deposits in the fuel system of an internal combustion engine,the method comprising using as the fuel for the internal combustionengine the fuel compositions described above. The dispersant compoundsof the present application can be present in the fuel in an amountsufficient to reduce the deposits in the fuel system. Deposits may bereduced as compared to the amount of deposits that would occur in thesame fuel system operated in the same manner and using the same fuelcomposition, if the fuel composition were devoid of the dispersantcompound.

In one aspect, the present application is directed to a method ofdispersing soot in a base fuel. The method comprises providing to acombustion system the fuel compositions of the present application,wherein the dispersant compound is present in the base fuel in an amountsufficient to maintain at least some soot in suspension in the base fuelfor a period of time longer than if the base fuel did not contain thedispersant compound.

The following Examples are offered to specifically illustrate thisinvention. These Examples and illustrations are not to be construed inany way as limiting the scope of this invention.

EXAMPLES Example 1A

To a 1 L resin kettle was charged 43.8 g of ethylenediamine tetraaceticacid and 370 mL of water. The resulting suspension was stirred andheated at 100° C. TEPA (113.4 g) was added via an addition funnel, andthe reaction mixture was stirred and heated under nitrogen for 3 hours.The suspension turned to a yellow solution upon addition of the amine.The water was removed in vacuo from the reaction mixture to afford 156 gof yellow viscous oil. This intermediate was diluted with 100 g of waterand transferred to a jar.

A proposed intermediate for the process of Example 1A is shown as theproduct of the reaction illustrated below:

where R²⁰ and R²¹ can be independently chosen from OH, TEPA, and TEPAsalt (O⁻⁺H-TEPA).

Example 1B

To a 3 L resin kettle equipped with an overhead stirrer was charged 951g of a 1250 Mn PIBSA. The PIBSA was heated to 160° C. and stirred undernitrogen. Then 248.1 g of the intermediate from Example 1A was added viaan addition funnel over a 1 hour period. The reaction mixture wasstirred and heated for 3 hours under reduced pressure. The reactionmixture was diluted with 880 g of process oil and filtered to afford1800 g of the desired product.

A proposed reaction for the process of Example 1B is illustrated below:

where 'R²⁰ and 'R²¹ can be independently chosen from TEPA succinimideand TEPA succinimide salt.

Example 2

The additive of Example 1B was blended into a passenger car motor oilformulation utilizing other components, including metal-containingsulfonates, zinc dithiophosphate wear inhibitors, sulfur containingantioxidants, diaryl amine and phenolic antioxidants, oleate andmolybdenum friction modifiers, a pour point depressant, a viscosityindex improver (HiTEC®5751) and a lubricating base oil. These othercomponents were in concentrations typically found in fully formulatedmulti-grade passenger car motor oils.

The kinematic viscosity at 100° C. (KV100) (mm²/s) and cold crankingsimulator viscosity at 30° C. (CCS-30) (centipoise) were determined andthe results are shown in Table 1 below.

TABLE 1 5W 30 Blend Study Results Dispersant KV100 CCS-30 Example 1B11.28 5895

Example 3

In Table 2 below, the sludge containing properties of a lubricantcontaining the dispersant of example 1B, as described above, and acomparative lubricant containing a commercially available dispersantwere compared using the Sequence VG engine test (an industry dispersantsludge test), to determine average engine sludge (“AES”), rocker coversludge (“RCS”), piston skirt varnish (“PSV”), and average engine varnish(“AEV”). The lubricants used were fully formulated lubricants. In eachsample, the ingredients of the lubricant are exactly the same except forthe dispersant.

The Sequence VG engine sludge and varnish deposit test is a firedengine-dynamometer test that evaluates the ability of a lubricant tominimize the formation of sludge and varnish deposits. The test methodwas a cyclic test, with a total running duration of 216 hours,consisting of 54 cycles of 4 hours each. The test engine was a Ford 4.6L, spark ignition, four stroke, eight cylinder “V” configuration engine.Features of this engine include dual overhead camshafts, a cross-flowfast burn cylinder head design, two valves per cylinder, and electronicport fuel injection. A 90-minute break-in schedule was conducted priorto each test, since a new engine build is used for each test. Upon testcompletion, the engine was disassembled and rated for sludge. Averageengine sludge was calculated for each sample.

The results of this testing are shown in Table 2. The pass limits foreach performance measure are also indicated in the table.

TABLE 2 Sequence VG Engine Test Results Dispersant Code AES RCS AEV PSVExample 1B 8.91 9.54 9.22 8.02 Comparative 7.91 9.25 8.90 7.64 Passlimits 7.80 8.00 8.90 7.50

As shown from Table 2 above, the lubricant containing the dispersant ofExample 1B not only passed each performance measure, but resulted inhigher AES, RCS, AEV and PSV test scores than the Comparative Example A.The results of this test indicate improved performance of the dispersantof the present application.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Accordingly, unless indicated to the contrary, thenumerical parameters set forth in the following specification andattached claims are approximations that can vary depending upon thedesired properties sought to be obtained by the present disclosure. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claims, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

It is noted that, as used in this specification and the appended claims,the singular forms “a,” “an,” and “the,” include plural referents unlessexpressly and unequivocally limited to one referent. Thus, for example,reference to “an acid” includes two or more different acids. As usedherein, the term “include” and its grammatical variants are intended tobe non-limiting, such that recitation of items in a list is not to theexclusion of other like items that can be substituted or added to thelisted items.

While particular embodiments have been described, alternatives,modifications, variations, improvements, and substantial equivalentsthat are or can be presently unforeseen can arise to applicants orothers skilled in the art. Accordingly, the appended claims as filed andas they can be amended are intended to embrace all such alternatives,modifications variations, improvements, and substantial equivalents.

What is claimed is:
 1. A process for forming a dispersant compoundcomprising: (i) reacting a polycarbonyl compound of formula I having atleast three carbonyl functions with a primary amine moiety of apolyamine of formula II to form a polyamine polyamide intermediate; and(ii) reacting the polyamine polyamide intermediate with a hydrocarbylcarbonyl compound of formula IV, wherein formula I is:

where n ranges from 0 to 4, and where R¹, R², R³, R⁴ and R⁵ areindependently chosen from a hydrogen atom and C₁ to C₁₀ linear orbranched alkyl groups, wherein formula II is:

wherein R⁶ is a hydrogen atom or an alkyl group having from 1 to 6carbon atoms, m is an integer ranging from 1 to 3, and n is an integerranging from 2 to 10, wherein a mole ratio of polycarbonyl compound topolyamine of formula II ranges from about 1:3 to about 1:5 to providethe polyamine polyamide dispersant intermediate compound of formula III,

where n ranges from 0 to 4, and R⁹, R ¹⁰, R¹¹, R¹²and R¹³ areindependently chosen from OH, a polyamine group, or a amine salt of thepolyamine group, with the proviso that at least three of R⁹, R¹⁰,R¹² andR¹³ are polyamine groups, and wherein formula IV is:

wherein R¹⁴ is a hydrocarbyl group.
 2. The process of claim 1, whereinR¹⁴ is polyisobutene.
 3. A polyamine polyamide dispersant intermediatecompound formed by reacting a polycarbonyl compound of formula I havingat least three carbonyl functions with a primary amine moiety of apolyamine of formula II, wherein formula I is:

where n ranges from 0 to 4, and where R¹, R², R³, R⁴ and R⁵ areindependently chosen from a hydrogen atom and C₁ to C₁₀ linear orbranched alkyl groups, and wherein formula II is:

wherein R⁶ is a hydrogen atom or an alkyl group having from 1 to 6carbon atoms, m is an integer ranging from 1 to 3, and n is an integerranging from 2 to 10, wherein a mole ratio of polycarbonyl compound toprimary amine compound ranges from about 1:3 to about 1:5 to provide thepolyamine polyamide dispersant intermediate compound of formula III,

where n ranges from 0 to 4, and R⁹, R¹⁰, R¹¹, R¹² and R¹³ areindependently chosen from OH, a polyamine group, or a salt of thepolyamine group, with the proviso that at least one of R⁹, R¹⁰, R¹¹, R¹²and R¹³ is a polyamine group.
 4. The polyamine polyamide dispersantintermediate compound claim 3, wherein the polyamine groups are selectedfrom the group consisting of diethylene triamine (DETA) groups,triethylene tetramine (TETA) groups, tetraethylene pentamine (TEPA)groups, pentaethylene hexamine (PEHA) groups, hexaethyleneheptamine(HEHA) groups, dipropylene triamine groups and tripropylene tetraminegroups, and salts of these groups.
 5. A method of forming a polyaminepolyamide intermediate compound, the method comprising reacting apolycarbonyl compound of formula I having at least three carbonylacylating functions with a primary amine moiety of a polyamine offormula II wherein formula I is:

where n ranges from 0 to 4, and where R¹, R², R³, R⁴ and R⁵ areindependently chosen from a hydrogen atom and C₁ to C₁₀ linear orbranched alkyl groups, and wherein formula II is:

wherein R⁶ is a hydrogen atom or an alkyl group having from 1 to 6carbon atoms, m is an integer ranging from 1 to 3, and n is an integerranging from 2 to 10, wherein a mole ratio of polycarbonyl compound topolyamine of formula II ranges from about 1:3 to about 1:5 to providethe polyamine polyamide dispersant intermediate compound of formula III,

here n ranges from 0 to 4, and R⁹, R¹⁰,R¹¹, R¹² and R¹³ areindependently chosen from OH, a polyamine group, or a amine salt of thepolyamine group, with the proviso that at least three of R⁹, R¹⁰, R¹¹,R¹² and R13 are polyamine groups.
 6. The method of claim 5, wherein thepolycarbonyl compound is chosen from ethylene diamine tetra acetic acid,diethylene triamine pentaacetic acid and esters of these acids.
 7. Themethod of claim 5, wherein the polyamine is selected from the groupconsisting of , diethylene triamine (DETA), triethylene tetramine(TETA), tetraethylene pentamine (TEPA), pentaethylene hexamine (PEHA),hexaethyleneheptamine (HEHA), dipropylene triamine and tripropylenetetramine.
 8. A process for forming a dispersant compound comprising:(i) reacting a hydrocarbyl carbonyl compound of formula IV with aprimary amine moiety of a polyamine of formula II to form amono-succinimide amine intermediate; and (ii) reacting themono-succinimide amine intermediate with a polycarbonyl compound offormula I having at least three carbonyl functions wherein thepolycarbonyl compound is a compound of formula I:

where n ranges from 0 to 4, and where R¹, R², R³, R⁴ and R⁵ areindependently chosen from a hydrogen atom and C₁ to C₁₀ linear orbranched alkyl groups, wherein the polyamine is a compound of formulaII:

wherein R⁶ is a hydrogen atom or an alkyl group having from 1 to 6carbon atoms, m is an integer ranging from 1 to 3, and n is an integerranging from 2 to 10, and wherein the hydrocarbyl carbonyl compound is acompound of the following formula IV:

wherein R¹⁴ is a hydrocarbyl group.
 9. The process of claim 8, whereinthe hydrocarbyl carbonyl compounds are chosen from hydrocarbylsubstituted succinic anhydrides, hydrocarbyl substituted succinic acids,and esters of hydrocarbyl substituted succinic acids.
 10. The process ofclaim 8, wherein R¹⁴ is polyisobutene.